Nucleophilic hydroalkylation

On the basis of previous results, the Rueping group started to study alkylations with activated alkenes and nucleophiles other than arenes. Recently, Lewis- and Brpnsted-acid-catalyzed hydroalkylation procedures with 1,3-dicarbonyl compounds as nucleophiles have been developed [69, 70]. These reactions primarily utilized Pd... 

Product predictions for nucleophilic additions to C q, based on AMI calculations, show that among the many possible isomers a few are energetically favored [29]. Two areas within the molecule can be distinguished, which are the inert belt at the equator and the more reactive CgQ-like double bonds at the poles (Figure 3.4). Experimentally, hydroalkylation and hydroarylation reactions of C q under quantitative HPLC control yield predominantly one isomer of each C7oHR[4]. 

Several examples of gold-catalyzed addition reactions of carbon nucleophiles to unactivated alkenes have been reported in recent years. Yao and Li obtained adducts with high regioselectivity from 3-diketones and various alkenes (styrene derivatives, conjugated dienes, enol ethers) in the presence of cationic gold species prepared in situ from AuCls and AgOTf (Scheme 4-15). This hydroalkylation is... 

Sames and coworkers have very recently introduced BF3 OEt2 catalysis to promote room temperature hydroalkylation of electron deflcient olefins as a formal sp C-H functionalization process. Coordination of the Lewis acid to the alkene moiety of the tetrahydropyran (121) facilitates a 1,5-hydride shift to afford a zwitterionic species, (122), which is followed by nucleophilic attack at the oxocarbonium center to furnish the requisite spirocyclic pyran (123) (Equation 74) [77]. 

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